FABRICATION AND CHARACTERIZATION OF COMPOSITE MEMBRANES FOR GAS SEPARATION JIANG LANYING NATIONAL UNIVERSITY OF SINGAPORE 2005 FABRICATION AND CHARACTERIZATION OF COMPOSITE MEMBRANES FOR GAS SEPARATION JIANG LANYING (B. Sci., Wuhan University, P. R. China) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHYLOSPHY DEPARTMENT OF CHEMICAL AND BIOMOLECULAR ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2005 ACKNOWLEDGEMENT First of all, I am deeply indebted to Prof. Chung. He has given me every opportunity to learn about membrane science and provide the essential facilities to carry out my research. His enthusiasm, positive outlook and belief in my abilities kept me going through the most difficult phase of research. Moreover, his mentoring and his attitude towards work are helpful to my growth and development in areas extending beyond research work. I may also like to express my appreciation to my Ph. D. thesis committee members, Prof. K. C. Loh, and Prof. L. Hong. Their suggestions on my Ph. D. proposal were constructive throughout my candidature in NUS. They were also helpful in providing experimental equipments for my work. Special thanks are due to all the team members in Prof. Chung’s research group. Dr. C. Cao and Dr. D. F. Li are especially recognized for their guidance and help in my initial step in hollow fiber spinning in the lab. Special thanks go to Dr. Z. Huang for providing the zeolite beta that is indispensable to my research. The suggestions on permeation cell set-up and modification from Ms. M. L. Chng, Dr. P. S. Tin were precious. All the members in Prof. Chung’s group are kind and helpful to me, which have made my study in NUS enjoyable and memorable. They include Dr. H. M. Guan, Mr. K. Y. Wang, Mr. J. Y. Xiong, Mr. Y. C. Xiao, Miss M. M. Teoh, Ms. X. Y. Qiao, Mr. Y. Li, Mr. Y. E. Santoso, and Miss W. Natalia. i Appreciation also goes to the staff in the Department of Chemical and Biomolecular Engineering that have helped me in various characterization techniques and given me professional suggestions. I would also like to convey my thanks to Dr. S. Kulprathipanja from UOP LLC for his valuable advices in my work on mixed matrix membranes and zeolites. Thanks also go to NUS and UOP LLC for the financial support with the grant number of R-279-000-108112, R-279-000-140-592, and R-279-000-184-112. Last but not the least, I must express my special thanks to my husband, Feng Zhao, for his unwavering and unconditional love and support. My parents and parents’ in-law also deserve the special recognition for their love and continuous encouragement and support. Lanying Jiang ii TABLE OF CONTENTS ACKNOWLEDGEMENT……………………………………………………………… .i TABLE OF CONTENTS…………………………… .…………… …………… .….iii SUMMARY………………………………………………………………………………x NOMENCLATURE…………………………………………………………………….xiii LIST OF TABLES…………………………………………………………….………xviii LIST OF FIGURES………………………………………………………….…….… .xx CHAPTER INTRODUCTION…………………………………………………………1 1.1 Membrane-based gas separation and its history…………………………………3 1.2 commercial applications for gas separation membranes……………………… .9 1.2.1 Nitrogen and oxygen enriched air……………………………………… 1.2.2 Natural gas treatment………………………………………………….….10 1.2.3 Hydrogen recovery……………………………………………………… 11 1.2.4 Other potential applications ………………………………………… .…12 1.3 Principles in gas separation membrane production…………………………….13 1.3.1 Material selection…………………………………………………… .….13 1.3.2 Membrane formation and modification…………………………….…….20 1.3.2.1 Membrane formation …………………………………… .……20 1.3.2.2 Membrane modification………………………………….… ….25 1.3.3 Membrane module design………………………………………… .……27 1.4 Research objectives…………………………………………………………… 29 iii 1.5 Organization of research………………………………………………… ……31 CHAPTER THEORY AND BACKGROUND…………………………………… …34 2.1 Materials and transport mechanisms……………………………………… … 34 2.1.1 Amorphous polymers………………………………………………… …34 2.1.2 Zeolites and carbon molecular sieves……………………………….……39 2.1.3 Polymer/zeolite mixed matrix materials …………………………………46 2.1.3.1 Material selection…………………………………………………46 2.1.3.2 Steady-state permeability prediction by Maxwell Model…… .…47 2.1.3.3 Factors leading to non-ideal performance of the mixed matrix Membranes……………………………………………………… 49 2.2 Polymeric asymmetric membrane formation and modification…………… .…52 2.2.1 Phase inversion mechanism……………………………………… .…….52 2.2.1.1 Nucleation and growth……………………………………………55 2.2.1.2 Spinodal decomposition………………………………………… 56 2.2.2 Membrane formation……………………………………………… ……57 2.2.2.1 Phase inversion types………………………………………… …57 2.2.2.2 Skin layer and sublayer formation………………………… ……60 2.2.3 Membrane modification and Resistance model……………………… …61 2.3 Fabrication of hollow fibers……………………………………………… ….63 2.4 Mixed matrix membrane formation and modification…………………… ….67 CHAPTER EXPERIMENTAL PROCEDURES………………………………… .….72 iv 3.1 Single and dual-layer hollow fiber preparation……………………………… .72 3.2 Characterizations of gas transport properties ………………………………… 74 3.2.1 Pure gas permeation …………………………………………………… .74 3.2.2 Mixed gas permeation…………………………………………… …… .81 3.3 Characterization of physical properties…………………………………… …83 3.3.1 Field emission scanning electron microscopy (FESEM) and scanning electron microscopy (SEM)…………………………… …… 83 3.3.2 Others…………………………………………………… .……….…….84 CHAPTERR FABRICATION OF MATRIMID/POLYETHERSULTONE DUALLAYER HOLLOW FIBER MEMBRANES FOR GAS SEPARATION……………………………………………………… .87 4.1 Introduction……………………………… .…………………………….….…87 4.2 Experimental…………………… .……………………………………………90 4.2.1 Materials……………………… …………………………………… …90 4.2.2 Dope formulation………………………………………………….…… 91 4.2.3 Co-extrusion of the dual-layer hollow fiber membranes and solvent exchange…………………………………………………………… .….93 4.2.4 Gas permeation experiments…………………………………………… 94 4.2.5 Characterization…………………………………………………… .… 94 4.3 Results and discussion………………………………………… …………… 95 4.3.1 Effect of spinning temperature on the separation performance… .…… 95 4.3.2 Membrane morphology and macrovoids formation………………… 96 v 4.3.3 Interlayer diffusion phenomenon…………………………………… .103 4.3.4 Effect of dope flow rate on the gas separation performance……… ….104 4.3.5 Mixed gas separation……………………………………………… ….106 4.4 Conclusion……………………………………………………………… … 108 CHAPTER CARBON-ZEOLITE COMPOSITE MEMBRANES FOR GAS SEPARATION…………………………………………………….……109 5.1 Introduction………………………………………………………………… .109 5.2 Experimental…………………………………… ………………………… .112 5.2.1 Materials and preparation of polymer precursors………………………112 5.2.2 Preparation of Polymer-zeolite Mixed Matrix Membranes and carbon membranes…………………………………………………………… .112 5.2.3 Gas permeation measurement………………………………………….115 5.3 Results and discussion……………………………………………………… 116 CHAPTER FUNDAMENTAL UNDERSTANDING OF NANO-SIZED ZEOLITE DISTRIBUTION IN THE FORMATION OF THE MIXED MATRIX SINGLE- AND DUAL-LAYER ASYMMETRIC HOLLOW FIBER MEMBRANES…………………………………………………… .….122 6.1 Introduction…………………………………………………………… …….122 6.2 Experimental…………………………………………………………….……125 6.2.1 Materials…………………………………………………………….….125 6.2.2 Dope preparation……………………………………………………….125 vi 6.2.3 Hollow fiber spinning……………………………………………… …126 6.2.4 Characterization…………………………………………………… ….127 6.3 Results and discussion…………………………………………………….… 127 6.3.1 Analysis and hypothesis……………………………………………… 127 6.3.2 Single-layer mixed matrix hollow fibers……………………………… 132 6.3.3 Dual-layer mixed matrix hollow fibers………………………………….137 6.3.4 Preliminary data on gas permeance of the mixed matrix hollow fibers .143 6.4 Conclusion……………………………………………………………………145 CHAPTER INVESTIGATION AT REVITALIZING THE SEPARATION PERFORMANCE OF THE HOLLOW FIBERS WITH A THIN MIXED MATRIX COMPOSITE SKIN FOR GAS SEPARATION…………………………………………………….……147 7.1 Introduction ……………………………………………………………….….147 7.2 Experimental …………………………………………………………………149 7.2.1 Materials……………………………………………………………… 149 7.2.2 Hollow fiber fabrication……………………………………………… .151 7.2.3 Characterization……………………………………………………… .153 7.3 Results and discussion……………………………… .…………………… 153 7.3.1 Hollow fiber spinning and the separation performance of as-spun fibers…………………………………………………… ….…153 7.3.2 The effect of heat treatment on morphology and separation Performance…………………………………………………………….157 vii 7.3.3 The effect of surface coating on separation performance………………161 7.3.4 The effects of mixed matrix layer thickness on separation Performance…………………………………………………………….167 7.3.5 The performance of the hollow fiber at difference temperatures………170 7.4 Conclusion…………………………………………………………………… 172 CHAPTER A NOVEL APPROACH AT IMPROVING THE MORPHOLOGY AND PERFORMANCE OF POLYMER/ZEOLITE MIXED MATRIX HOLLOW FIBERS FOR GAS SEPARATION……………………… 174 8.1 Introduction……………………………………………………………….… 174 8.2 Experimental……………………………………………………………….…175 8.2.1 Materials……………………………………………………………… 175 8.2.2 Hollow fiber fabrication……………………………………………… 176 8.2.3 Post-treatment of hollow fibers and coating……………………………177 8.2.4 Characterization……………………………………………………… .179 8.3 Results and discussion…………………………………………………… .…179 8.3.1 Morphology of as-spun hollow fibers……………………………….… 179 8.3.2 Morphological changes with different post-treatment procedures ….….181 8.3.3 Pure gas permeation properties as a function of post-treatment procedures and zeolite loading…………………………………………………… .187 8.3.4 Physical characterization of the mixed matrix hollow fibers and zeolite beta particles……………………………………………………………197 8.4 Conclusion…………………………………………………………………….198 viii Wernick D. L., E. J. Osterhuber, Permeation through a single crystal of zeolite NaX. J. Membr. Sci., 22 (1985) 27. Wienk I. M., R. M. Boom, M. A. M. Beerlage, A. M. W. Bulte, C. A. Smolders, H. Strathmann, Recent advances in the formation of phase inversion membranes made from amorphous or semi-crystalline polymers, J. Membr. Sci., 113 (1996) 361. Wijmans J. G., J. Kant, M. H. V. Mulder, C. A. Smolders, Phase separation phenomena in solutions of polysulfone in mixture of a solvent an non-solvent: Relationship with membrane formation, Polymer, 26 (1985) 1539. Wolf B. A., Thermodynamic theory of flowing polymer solutions and its application to phase separation, Macromolecules, 17 (1984) 615. Yanagimoto T., Manufacture of ultrafiltration membranes, Japanese Patent 62019205, 1987. Yang S. H., W. K. Teo, K. Li, Formation of annular hollow fibers for immobilization of yeast in annular passages, J. Membr. Sci., 184 (2001) 107. Yilmza L., J. McHugh, Analysis of nonsolvent-solvent-poloymer phase diagrams and their relevance to membrane formation modeling, J. Appl. Polym. Sci., 31 (1986) 997. Yong T. H., L. W. Chen, A two mechanism of diffusion controlled ethylene vinyl alcohols membrane formation, J. Membr. Sci., 57 (1991) 69. Yong H. H., H. C. Park, Y. S. Kang, J. Won, W. N. Kim, Zeolite-filled polyimide membrane containing 2, 4, 6-triaminopyrimidine, J. Membr. Sci., 188 (2001) 151. Zeman L., G. Tkacik, Thermodynamic analysis of a membrane-forming syster water/Nmethyl-2-pyrrolidone/polyethersulfone, J. Membr. Sci., 36 (1988) 119. 234 Zhang X. F., W. Q. Zhu, H. O. Liu, T. H. Wang, Novel tubular composite carbon-zeolite membranes, Mater. Lett., 58 (2004a) 2223. Zhang L. X., K. E. Gilbert, R. M. Baldwin, J. D. Way, Preparation and testing of carbon/silicalite-1 composite membranes, Chem. Eng. Comm., 191 (2004b) 665. Zimmerman C. M., A. Singh A, W. J. Koros, mixed matrix composite membranes for gas separations, J. Membr. Sci., 137 (1997) 145. 235 APPENDIX A ZEOLITE BETA (β) SYNTHESIS AND CHARACTERIZATION (CHAPTER 6, 7, 8) A.1 SYNTHESIS OF ZEOLITE β Zeolite β can be synthesized using many different methods, dependent on the silica sources used. The method employed here was similar to that reported by Borade et al. (Borade and Clearfield, 1996). In the synthesis in our lab, the batch composition was 1.5Na2O: 1.0Al2O3: 10TEAOH: 30SiO2: 245H2O, which was slightly different from that of (Borade and Clearfield, 1996). Based on the above formula, 1.546g sodium aluminate (Na2O, 33.2 wt%, Na2O/Al2O3=1.5) was measured and put into a 250ml beaker; the sodium aluminate was dissolved in 8ml DI water under constant stirring. The clear salt solution thus formed was then added with 19ml tetraethyl ammonium hydroxide (TEAOH, 40 wt% aqueous solution, 1.06g/ml) and 5ml of DI water balance while stirring. 15 minutes later, 10.0 g fumed silica was added into the resultant solution under stirring; the mixture initially appeared to be a dry powder but turned into a very dense and homogeneous gel after about 3-hour stirring. The viscous gel was transferred into a 200ml Teflon container that was set in a stainless steel autoclave. The crystallization of zeolite β was carried out at 170oC under an autogenous pressure for 24-48 hours. The autoclave was directly quenched with tap water after taken out from the oven. The resultant product was thoroughly washed with DI water till a PH value of 8.5 and then 236 was centrifuged at 10000 circles/minute for minutes to extract The powders. The final product was dried at 70oC for 12 hours. A.2 TEMPLATE REMOVAL FROM FRESHLY PREPARED ZEOITES Zeolite materials are generally synthesized by using self-assembling organic surfactants that serve as the template. After synthesis, the template must be removed to form the sieve pore prior to any potential applications. Conventionally, the organic template is removed by high temperature calcinations; however, with such method, the organic template is directly burned off and the final particles might form agglomerates. In this sense, the synthesized zeolites are large zeoite crystals which are not suitable to prepare homogeneous zeolite suspension to develop practical composite membranes with polymer matrix. Recently, Wang et al. (Wang et al., 2002a) proposed a polymer-networking method as a supplement to the conventional procedure for template removal; by applying a certain polymer-net work in the particle suspension/around the particles, the zeolite aggregations can be avoided. Therefore, this novel method was adopted in our method with some trivial modifications in order to prevent nanocrystal aggregation. Firstly, the washed zeolites were dispersed into DI water by using an oscillator. The monomer (acrylamide), crosslinker (N, N’-methylenebisacrylamide) and initiator ((NH4)2S2O8) were added into the zeolite particle suspension under agitation. Typically, 1.0 g monomer, 0.1mg/g crosslinker and 25mg/g initiator was added into a 10-g zeolite water suspension which 237 contains around wt. % zeolite. Then, the resultant mixture was stirred for 30 minutes before heated to 70oC for polymerization. The crosslinked elastic hydrogel was dried in air at 90oC overnight. Thereafter, the obtained solid polymer-zeolite composite was directly calcinated at 550oC for 10 hours at a scanning rate of 5oC/min to remove the template and polymer in air. The approach proposed by Wang et al. (Wang et al., 2002a) was first doing carbonization at 500oC under N2 followed by calcinations under O2. Fig. A.1 shows the framework of zeolite beta. Fig. A.2 displays the FESEM pictures and XRD pattern of the synthesized beta. Fig. A.3. is the particle size determined by the laser light scattering (LLS) system. Channels: 12 6.6 x 6.7** ↔ [001] 12 5.6 x 5.6* 12-ring viewed along Framework viewed along [010]. (a) 12-ring viewed along [001] (b) Fig. A.1. Framework (a) and channels (b) of the zeolite beta (http://www.iza-structure.org/databases/)*. * http://www.iza-structure.org/databases/ (This website was designed and implemented by Ch. Baerlocher in collaboration with L. B. McCusker). 238 Intensity Experimental Reference [1] o theta ( ) (a) (b) Fig. A.2. FESEM picture (a) and XRD pattern (b) of the self-synthesize zeolite beta. Fig. A.3. The zeolite beta particle size determined by Laser light scattering (LLS). REFERENCES Borade R. B., A. Clearfield, Preparation of aluminum-rich Beta zeolite, Microporous Mater., (1996) 289. Wang H., B. A. Holmberg, Y. Yan, Homogeneous polymer-zeolites nano composite membranes by incorporating dispersible template-removed zeolite nanoparticles, J. Mater. Chem., 12 (2002) 3640. 239 APPENDIX B A NEW TESTING SYSTEM TO DETERMINE THE O2/N2 MIXED GAS PERMEATION THROUGH HOLLLOW FIBERS WITH AN OXYGEN (CHAPTER 7) B. SYSTEM DESCRIPTION AND MEASUREMENT PROCEDURE A schematic diagram of apparatus using the oxygen analyzer for O2/N2 mixed gas permeation test through hollow fiber membranes was shown in Fig. B.1. Stainless steel components such as tubing, union tees and connectors were used in the construction of testing system. A hollow fiber module was attached in a shell feed method of operation. This module was made by assembling some pieces of fibers into a bundle. One end of the bundle was sealed with a 5min rapid epoxy resin (Araldite®, Switzerland), while the shell side of the other end was glued onto the Swagelok VCR® union tee using a regular epoxy resin (Eposet®). It took 8h to fully cure the Eposet® resin. Two membrane modules with different polymers were tested in this work. The module specifications and experimental conditions are summarized in Table B.1. Purified air including 21%±1% O2 was used as the feed gas and was pushed to the shell side of hollow fiber membranes continuously from a compressed gas cylinder shown in Fig. B.1. 240 Feed outlet Mass flow controller (2) inlet outlet O2 analyzer inlet Needle valve Needle valve Needle valve Atmospher outlet Mass flow controller (1) inlet e Needle valve Vacuum pump Pressur e gauge Retentat e 5-minute epoxy Permeat e 73.7mm A module with some pieces hollow fibers VCR Union Tee Bubble flow meter 8-hour Gas reservoir Needl e valve Gas cylinder (pure air) Inner diameter: 10.2mm Fig. B.1. Schematic diagram of apparatus for O2/N2 mixed gas permeation test through hollow fiber membranes using the oxygen analyzer. A very small part of feed gas went through the wall of hollow fiber membranes and entered the permeate side, while most of feed gas entered the retentate side from the midarm of union tee. The feed gas pressure was controlled by the needle valve and shown by a digital pressure gauge. The feed gas pressure was adjusted to be 200psig (relative pressure) for the air test and the permeate side was open to atmosphere in this study. The system was run at ambient temperature. The whole measurement procedure comprised four steps to determine the apparent permeance of each species and selectivity in an O2/N2 mixed gas. The first step was to decide the retentate and permeate flow rates by a mass flow controller and bubble flow meter, respectively. The model of mass flow controller used in this work was GFC 17 241 (Aalborg®), which cost S$1,740 including calibration. Its measurement range was 010ml/min (under standard temperature and pressure). For different gases, the actual flow rate was the reading of mass flow controller times an adjustable coefficient because this equipment was calibrated with N2 as received. In our case, the adjustable coefficient is approximately equal to for air because the adjustable coefficient is for N2 and 0.996 for O2. Firstly, the reading of mass flow controller (1) was randomly set at a certain value, for example 2ml/min. Secondly, the permeate flow rate was measured by the bubble flow meter shown in Fig. B.1. If the ratio of permeate flow rate to retentate flow rate was around 0.05 (i.e. the stage cut was slightly less than 0.05), the first step (i.e. measurement of flow rates) was finished. Otherwise, the reading of mass flow controller (1) would be readjusted until this requirement was achieved to eliminate the effect of concentration polarization (O’Brien et al., 1986; Wang et al., 2002b). In this work, the ultimate retentate and permeate flow rates in the air test were 0.50 and 0.0219ml/min for hollow fiber 1, respectively; and 0.57 and 0.0283ml/minfor hollow fiber were ml/min, respectively, shown in Table B.1. Table B.1. Hollow fiber module specifications and experimental conditions. Membrane name Hollow fiber Hollow fiber Membrane material polyethersulfone polysulfone Outer diameter of fibers (μm) Inner diameter of fibers (μm) length of fibers (cm) number of fibers Compositions of mixed gas 950 520 5.5 11 1000 550 4.5 21%±1% O2 in air or CO2/CH4 (50/50%) 21%±1% O2 in air or CO2/CH4 (50/50%) 242 Feed gas pressure (psig) (relative value) Permeate gas pressure (psig) (relative value) Temperature (oC) Retentate flow rate (ml/min) Permeate flow rate (ml/min) 200 (in air) or 190 (in CO2/CH4) 200 (in air) or 200 (in CO2/CH4) 24 0.50 (in air) or 1.38 (in CO2/CH4) 0.0219 (in air) or 0.0819 (in CO2/CH4) 24 0.57 (in air) 2.70 (in CO2/CH4) 0.0283 (in air) 0.135 (in CO2/CH4) The second step was to measure the composition of retentate gas using the oxygen analyzer. The Advanced Micro Instrument (AMI) trace oxygen analyzer model 201 was applied in this study. The analyzer cost S$5500, inclusive of the installation fee. Its measurement range was 0-100% O2 concentration. Because the retentate flow rate was too small, it was impossible to produce a high positive pressure from the inlet to outlet of O2 analyzer to prevent the interference of atmosphere entering into the O2 analyzer. Addressing this problem, a special design was made here. Another mass flow controller (2) was connected with the O2 analyzer shown in Fig. B.1. The gas can only flow from the inlet to outlet in the mass flow controller and cannot flow inversely due to its special inner structure; therefore, the gas in atmosphere could not diffuse into the system. After opening the needle valves 2, and and closing the needle valve 4, the line from the outlet of mass flow controller (1) to the outlet of mass flow controller (2) was evacuated to remove residual gas. The electric power of O2 analyzer must be shut down during this period; otherwise, this action may damage the sensor of O2 analyzer by boiling the electrolyte. Thereafter, the needle valves and were closed and the electric power of O2 analyzer was turned on. Thereupon, the retentate gas accumulated inside the O2 analyzer indicated by a gradual increase in the reading of O2 analyzer. After an appropriate period 243 of time, needle valves and were opened and the superfluous gas stored in the O2 analyzer streamed into the atmosphere through the mass flow controller (2). The reading of mass flow controller (2) should be regulated to a value slightly higher than that of the mass flow controller (1). With a decrease in the superfluous gas contents in the O2 analyzer, the reading of mass flow controller (2) diminished gradually until it was the same with that of the mass flow controller (1) (i.e. 0.5ml/min for hollow fiber and 0.57 ml/min for hollow fiber 2). At this time, the stable reading of O2 analyzer was just the O2 concentration in the retentate gas. The third step was to measure the composition of feed gas by using the O2 analyzer again and then calculate the composition of permeate gas through the mass balance. In this study, the composition of permeate gas was not measured directly by using the O2 analyzer because the permeate flow rate was so small that a much larger error may be introduced during the measurement. The tubing of feed gas was connected directly with the inlet of mass flow controller (1) illustrated in Fig. B.1. and the composition measurement was similar to that of the retentate gas. The last step was that the apparent permeance of each species in the O2/N2 mixed gas was calculated based on one set of differential equations developed by Wang et al. (2002b), in which the non-ideal gas behavior and pressure drop inside the hollow fiber have been considered. In the case of negligible permeate gas pressure, the selectivity of hollow fiber membranes for a mixed gas was equal to the ideal selectivity; that is, it can be calculated from the ratio of multicomponent permeances measured at the partial pressure (Wang et 244 al., 2002b; Koros et al., 1981; Tin et al., 2003). B. RESULTS The performance of this new testing system is evaluated by measuring the permeance of two types of hollow fiber membranes in the mixed gas. The permeance of pure gas can be measured using the similar technique from Jones and Koros (Jones and Koros, 1994). O2/N2 separation results of mixed gas and pure gas are listed in Table B.2. Table B.2. Comparison of separation performance for hollow fiber membranes between the O2/N2 mixed gas and pure gas measurements. Membrane Mixed gas (21%±1% O2 in air) at 24oC name Total Selectivity Permeance feed (O2/N2) (GPU) pressure O2 N2 (pisg) Hollow 200 0.0631 0.00918 6.87 fiber Hollow 200 0.271 0.0423 6.4 fiber Pure gas at 35oC Permeance (GPU) O2 N2 Ideal selectivity (O2/N2) 0.0741 0.0114 6.50 0.306 0.0493 6.2 Pure O2 and N2 gases were tested at 132 psig (relative pressure). It can be found that both permeance and selectivity of mixed gas are very close to those of pure gas when considering the effect of different testing temperatures. The results demonstrate that the new testing system devised in this work can effectively determine the permeance and selectivity of hollow fiber membranes in the separation of O2/N2 mixed gas. The total price of apparatus applied in this new testing system including one 245 oxygen analyzer, two mass flow controllers and one bubble flow meter is no more than S$10,000 which is much lower than that of GC-MSD apparatus. In order to further prove the authenticity of O2/N2 mixed gas permeation results measured by the O2 analyzer, the same hollow fiber samples were used to separate the CO2/CH4 (50/50%) mixture. The testing procedure was similar to that applied in the air separation and the composition of CO2/CH4 mixed gas is determined by GC instead of the O2 analyzer. Experimental conditions and parameters can be found in Table B.1. CO2/CH4 separation results of mixed gas and pure gas are given in Table B.3. It can be seen that the difference between mixed gas and pure gas was almost negligible if considering the effect of different testing temperatures, which again justify that this new testing system with the much lower cost can fulfill the purpose to measure O2/N2 mixed gas separation performance through the hollow fiber membranes. Table B.3. Comparison of separation performance for hollow fiber membranes between the CO2/CH4 mixed gas and pure gas measurements. Membr. ID Mixed gas (50/50% CO2/CH4) at 24oC Permeance Total (GPU) feed pressure CO2 CH4 (pisg) Hollow 190 0.164 0.00485 fiber Hollow 200 0.807 0.0249 fiber Pure gas at 35oC Selectivity (CO2/CH4) Permeance (GPU) CO2 CH4 Ideal selectivity (CO2/CH4) 33.8 0.187 0.00641 29.2 32.4 0.835 31.2 0.0267 Pure CO2 and CH4 gases were tested at 100psig (relative pressure). 246 REFERENCES Jones C. W., W. J. Koros, Carbon molecular sieve gas separation membrane. 1. Preparation and characterization based on polyimide precursors, Carbon, 32 (8) (1994) 1419. Koros W.J., R. T. Chern, V. T. Stannett, H.B. Hopfenberg, A model for permeation of mixed gases and vapors in glassy polymers, J. Polym. Sci. Polym. Phys. Ed., 19 (1981) 1513. O'Brien K. C., W. J. Koros, T. A. Barbari, E.S. Sanders, "A new technique for the measurement of multicomponent gas transport through polymer films", J. Membr. Sci., 29 (1986) 229. Tin P. S., T. S. Chung, Y. Liu, R. Wang, S. L. Liu, K. P. Pramoda, Effects of cross-linking modification on gas separation performance of Matrimid membranes, J. Membr. Sci., 225 (2003) 77. Wang R., S. L. Liu, T. T. Lin, T. S. Chung, Characterization of hollow fiber membranes in a permeator using binary gas mixtures, Chem. Eng. Sci. 57 (2002) 967. 247 PUBLICATIONS Journals: • Lanying Jiang, Tai-Shung Chung, Santi Kulprathipanja, A novel approach to fabricate mixed matrix hollow fibers with superior intimate polymer/zeolite interface for gas separation, Accepted by AIChE Journal. • Yi Li, Lanying Jiang, Tai-Shung Chung, A new testing system to determine O2/N2 mixed gas permeation through hollow fiber membranes with an oxygen analyzer, Industrial Engineering and Chemistry Research, 45 (2006) 871. • Lanying Jiang, Tai-Shung Chung, Santi Kulprathipanja, An investigation to revitalize the separation performance of hollow fibers with a thin mixed matrix composite skin for gas separation, Journal of Membrane Science, 276 (2006)113. • Pei Shi Tin, Tai-Shung Chung, Lanying Jiang, Santi Kulprathipanja Carbon- Zeolite Composite Membranes for Gas Separation, Carbon, 43 (2005) 2025. • Lanying Jiang, Tai-Shung Chung, Chun Cao, Zhen Huang, Santi Kulprathipanja, Fundamental understanding of nano-sized zeolites distribution in the formation of the mixed matrix single- and dual-layer asymmetric hollow fiber membranes, Journal of Membrane Science, 252 (2005) 89. 248 • Lanying Jiang, Tai-Shung Chung, Dong Fei Li, Chun Cao, Santi Kulprathipanja, Fabrication of Matrimid/polyethersulfone dual-layer hollow fiber membranes for gas separation Journal of Membrane Science, 240 (2004) 91. Patents: • Tai-Shung Chung, Lanying Jiang, Chun Cao, Santi Kulprathipanja, Mixed matrix dual-layer hollow fiber membrane and process for producing the same, US Patent publication (US 60/643129). • Pei Shi Tin, Tai-Shung Chung, Lanying Jiang, Santi Kulprathipanja, Carbon- Zeolite Mixed Matrix Composite Membranes for Gas Separation, US Patent publication (US 60/621946). 249 [...]... conditions…… 242 Table B.2 Comparison of separation performance for hollow fiber membranes between the O2/N2 mixed gas and pure gas measurements……… … 245 Table B.3 Comparison of separation performance for hollow fiber membranes between the CO2/CH4 mixed gas and pure gas measurements……… 246 xix LIST OF FIGURES Fig 1.1 Schematic diagram of membrane separation process of a two-components mixture………………………... volume for industrial gases has an expected annual growth of 4% in industrialized countries and 14% in Asia (CHEManager) The gas separation or purification is now primarily carried out by cryogenic separation, pressure swing adsorption and membrane separation In the past few decades membrane separation entered the gas separation territory previously occupied by the conventional cryogenic separation and. .. identification of novel membrane and separation process having higher efficiency and stability, the importance of this process to solve issues involving critical separation requirement such as refinery, petrochemical and natural gas treatment will increase Table 1.2 illustrates the predicted membrane gas separation markets [9] 2 Table 1.2 Future market of membrane gas separation (Baker, 2001) Separation. .. invention of coating asymmetric polysulfone membranes with silicon rubber effectively sealed the pinholes and led to first generation of commercial gas separation membrane, Prism or Prism Separator These separators are devices with a modular design and used for the separation of hydrogen from the product stream of ammonia synthesis and the oxo-alcohol process In the application of processing a purge gas. .. initiated based on the aforementioned fundamental works The problem of membrane thickness was first solved by Loeb and Sourirajan in 1963 (Loeb and Sourirajan, 1964) with the invention of asymmetric membranes These membrane have a thin dense skin of approximately 0.2 µm supported by a porous support and were applied for reverse osmosis Later, these membranes were applied for gas separation by modification... developments of gas separation membranes (Kesting and Fritzsche, 1993) Scientist (Year) Event Graham (1829) First recorded observation Mitchell (1931) Gas permeation through natural rubber Fick (1855) Von Wroblewski (1879) Law of mass diffusion Permeability coefficient product of diffusion and absorption coefficients Kayser (1891) Demonstration of validity of Henry’s Law for the adsorption of carbon dioxide... membrane-based gas separation process of a two-component mixture Upstream Membrane Feed Downstream Permeate l Fig 1.1 Schematic diagram of membrane separation process of a two-components mixture The history of membrane-based gas separation can be dated back to around 170 year ago when Thomas Graham observed gaseous osmosis for the air/carbon dioxide system through a wet animal bladder (Kesting and Fritzsche,... fibers…………….… 152 Table 7.3 Separation performance of the dual-layer hollow fibers………… … 155 Table 7.4 Heat treatment conditions for the hollow fibers……… .157 Table 7.5 Hollow fiber separation performance as a function of heat treatment before coating……………………………………………………… …159 Table 7.6 Hollow fiber separation performance as a function of heat treatment after coating and different coating approaches…………………………... purity, and consequently, the choice of the purification method; the feed property also influences the choice of the separation technology (Koros and Flemming, 1993) 1 The development of membrane separation market through 1996 to 2000 and expected growth rate are summarized in Table 1.1 Membrane-based gas separation accounts for US$ 250 million/per year as shown in this table The major applications of membrane... modules (cm), lI Void thickness of the inferface voids of mixed matrix membrane (Å) lφ Thickness of rigidified region of mixed matrix membrane (Å) lφ’ Thickness of reduced permeability region of mixed matrix membrane (Å) M Molecular weight (g/mole) MA Gas molecular weight (g/mole) Mw Gas molecular weight (g/mole) NA Steady state flux of the permeating gas at standard temperature and pressure (cm3 (STP)/s) . FABRICATION AND CHARACTERIZATION OF COMPOSITE MEMBRANES FOR GAS SEPARATION JIANG LANYING NATIONAL UNIVERSITY OF SINGAPORE 2005 FABRICATION AND CHARACTERIZATION OF. selectivity of component A over B  D i,j Ideal selectivity of a gas pair for diffusivity * i,j Ideal selectivity of a gas pair for permeability  S i,j Ideal selectivity of a gas pair for. COMPOSITE MEMBRANES FOR GAS SEPARATION JIANG LANYING (B. Sci., Wuhan University, P. R. China) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHYLOSPHY DEPARTMENT OF